GB2133030A - Azo dyestuffs - Google Patents

Abstract

Compounds of formula I <IMAGE> in which the symbols are defined in the specification, are useful as dyestuffs, particularly for paper and leather.

Description

SPECIFICATION Improvements in or relating to organic compounds The invention provides newazo compounds for use as dyestuffs for example on paper and cotton fabries.

According to the invention there is provided a compound offormula I or mixtures thereof

in which R is hydrogen or unsubstituted C1-4 alkyl; K is the residue of a benzthiazolyl substituted phenyl or of a coupling componentoftheacetoacety- lalkylamide series,the acetoacetylarylamide series, the pyridone series, the pyridine series, the di- or tri-amino pyridine series, the pyrazolone or amino pyrazole series, the cc-or ss-naphthol series, the aminophenyl series, the indole series, the carbazole series orthe barbituric acid series; and X0 is a direct bond or non-cationic bridging group attachedto Kora methylene bis-cationic bridging group attached to ring B or ring C; A0 is a non-chromophoric anion; wis-to1 ; tisOtol; p is 0,3 to 3, the values forw,tand p being average values in the case of mixtures; b is 1 or 2, providedthatwhen b=2, and X0 is a methylene bis-cationic bridging group p is in the range 0.3 - 1.5, and otherwise p is in the range 0.5 -3.

Rlis

ris0orl; R2aisC1-4alkyl ; R2 is a linear or branched C1 6alkyl group, unsubstituted or monosubstituted by a di(C1alkyl)amino group; or a linear or branched unsubstituted C3 6alkenyl group; R3 is hydrogen, a linear or branched unsubstituted C1-6alkyl group or a linear or branched C3 6alkenyl group;

Ais a direct bond our a bridging group; R5is hydrogen, C1-6alkyl unsubstituted or monosubstituted by phenyl, -CONH2 or -COO(C1-4alkyl) ; C2-6alkyl monosubstituted by CN, OH or halogen; -CH2-CH\o/-CH2; -CH2COCH3; unsubstituted cyclohexyl; or C3 6alkenyl group unsubstituted or monosubstituted by-OH or halogen.

R6 has a significance of R5 (independently of R6) or R5 and R6togetherwith the N-atom to which they are attached form a morpholine ring unsubstituted or substituted by 1 to 3 C14alkyl groups, a piperidine ring unsubstituted or substituted by 1 to 3 C14alkyl groups, a pyrrolidine ring unsubstituted or substituted by 1 to 3 C14alkyl groups or a piperazine ring unsubstituted or substituted by 1 to 3 C1-4alkyl groups; R5a has a non-cyclic significance of R5 (independently of R5) except hydrogen, and R6a has a non-cyclic significance of R6 (independently of R6) except hydrogen; and R7 is a linear or branched C1-4alkyl, unsubstituted or mono-substituted by halogen, OH, unsubstituted phenyl or-CONH2; or R5a and R6a together with the N-atom to which they are attached form a cyclic significance of R5 and R6; or R50, R6and R7 together with the N-atom to which they are attached form a pyridine group unsubstituted or substituted by 1 to 3 Alkyl groups; provided that when b is 1, then both R5 and R6 if present are otherthan hydrogen.

In this specification if a symbol appears more than once in a formula its significances are independent of one another unless indicated to the contrary.

Anyalkyl is preferably methyl or ethyl; anyalkoxy is preferably methoxy or ethoxy and any halogen is preferablychloro orbromo, more preferablythe former.

By the term methylene biscationic bridging group is meant a divalent bridging group linked by a methylene group at both ends to the rest ofthe moleculethe other bond of the methylene groups being attached to a cationic nitrogen atom.

Preferably K is K' where K' is defined below.

Preferably X0 is X0'where X0 is defined below.

Preferably b is 1.

Preferred compounds offormula I are offormula Il

in which R' is hydrogen, methyl or ethyl, R1,is

R2'a is methyl or ethyl; R2' is C14alkyl, unsubstituted or substituted by dimethylamino; R2' is hydrogen or unsubstituted linear or branched C1.4alkyl;

a C1-12alkylene group uninterrupted or interrupted by 1 or2 groups selected from -0--S-, and -N-R8 the C1-12alkylene group being unsubstituted or monosubstituted by-(CH2)m-N(R3')2 ; where mis an integer from 0 to 6 inclusive; Yis-HN-CO-HN-,-HN-CO-(CH2)m-CONH-,

R8 is hydrogen, unsubstituted C1.4alkyl; unsubstituted phenyl or unsubstituted naphthyl;

r11 is hydrogen, unsubstituted linear or branched c1-4-alkyl or unsubstituted phenyl; F5 is hydrogen; -CH2 #-CH-CH2--CH2-CO-CH3 ; linear or branched C1-4alkyl unsubstituted or monosubstituted by phenyl, -CON H2, -COO(C14alkyl); C2 4alkylene unsubstituted or monosubstituted by a group selected from Cl, Br, CN and OH; or C3-4alkenyl unsubstituted or monosubstituted by OH or Cl; R6' is hydrogen or linear or branched unsubstituted C14alkyl; or R5' and R6' together with the N-atom to which they are attached form an unsubstituted morpholine, piperidine, pyrrolidine or N-methyl piperazine group; Ra' has a non-cyclic significance of B5 except hydrogen, R6a' is unsubstituted C1.4alkyl and R7' is unsubstituted C1-4alkyl or benzyl; or R5a',R6a' and$-/ together with the N-atom to which they are attached form

where z is 0,1 or 2 and R36 is methyl or ethyl; K' is Kato K1 below

in which Ra is -N9R1a)2 or-N#(R2a)2R3aA# Ria is hydrogen, unsubstituted phenyl, unsubstituted cyclohexyl or Ct.12alkyl unsubstituted or monosubstituted halogen, CN, OH, phenyl or -CONH2; or both R1astogether with the N-atom to which they are attached form an unsubstituted piperidinee unsubstituted morpholine, unsubstituted piperazine, aC-unsubstituted N-(C1-4-alkyl) piperazine or unsubstituted or unsubstituted pyrrolidine; R2a has a non-cyclic or cyclic significance of Ria except hydrogen and R3a is unsubstituted C1.6alkyl or phenyl-C1-4alkyl; or both R2a sand R3as together with the N-atom to which they are attached form a pyridinium group, unsubstituted orsubstituted by 1 to 3 alkyl groups.

T is an unsubstituted C3-8alkenylene group or a linear or branched C1 12alkylene group, uninterrupted or interrupted by one -0-, -SO-or-N-R8group; R13 is a group offormula

R14 and R15independently of one another are unsubstituted C1-4alkyl or unsubstituted C14alkoxy; R16 is hydrogen, unsubstituted C14alkyl, unsubstituted benzyl of unsubstituted phenyl; R17 is hydrogen, -CN, -CONH2,

R18is hydrogen ;C1-4alkyl unsubstituted or or substituted by an unsubstituted phenyl group; -(CH2)2-CN; -(CH2)zOH; -(CH2}30CH3;

where R6a' and R7" a are as defined above; R19is hydrogen, unsubstituted C1-4alkyl, -(CH2)30CH3, -(CH2)20H, -(CH2)3N(CH3)2 or-( CH2)3N#(CH3)3A#; R20 is -OH or -NH2; R21 is unsubstituted C1.4alkyl or-CO-R31;

R27, R28, R29 independently of one another are selected from hydrogen, halogen, unsubstituted C1-4alkyl or unsubstituted C1-4alkoxy,-NO2 and CN ; R30 is unsubstituted C1-4alkyl,-CON(C1-4alkyl)2or -N(C1-4alkyl)2;

R32 and R33 independently of one another are selected from hydrogen, halogen, unsubstituted C1-4alkyl, unsubstituted C1-4alkoxy,-NO2 and-NH2 ; R34 is hydrogen or-NHCO(CH2)m-R39;;

R37 and R38 independently of one another are selected from hydrogen and unsubstituted C1-4alkyl;

K1 is a group offormula Ka to Kc or Keto K1(a (as defined under K' above); Xis 1,4-phenylene, 1,5-naphthylene, 2,7-flourene ora group offormula

where R40 is halogen, unsubstituted C14alkyl or unsubstituted C1-4alkoxy; Xa is any one of X1 to X64 X1 is a direct bond, X2 is a linear or branched C1-4alkyl group;

X63 -O-CH2-O-, X64 -CO-NH-R44-CO-NHwhere R41 is halogen, unsubstituted C1-4alkyl or unsubstltuted C1-4alkoxy; R42 is hydrogen or unsubstituted C1-4alkyl; R43 is halogen, -NH-CH2CH2OH or N(CH2CH2OH)2; R44 is a linear or branched unsubstituted C1 4alkylene group;; g is an integer from 1 to4 inclusive; Xb is X1, X2, X14, X21, or X34 defined above; X0' is X defined above attached to K' or is X0 where Xc is a group of the formula

where Rwa', A', R3' and rare as defined above, attached to ring B or ring C.

More preferred compounds offormula large of formula Ill

in which p' is 1 or 2.

Mixtures of compounds offormula Ill such that p' has an average value between 1 and 2, preferably approximately 1.5, are particularly preferred.

R2" is -CH3, -C2H5, -(CH2)2-N(CH3)2 or -(CH2)3 N(CH3)2; R3" is hydrogen or methyl; A" is a direct bond or -(CH2)a where a is an integer from 1 to 4 inclusive; or-CH2-CO-CH3;

or -CH2-CO-CH3 ; R6" is selected from-CH3 or-C2H5; R5a" and R6a" have a significance of R5" and R6" respectively (independently of R5" and R6") R7" is -CH3 or C2H5; K" is a group of one offormulae Kb' to K1'

where R1a' is hydrogen or unsubstituted C1-4alkyl; R13,is

R14' and R15' independently of one another are -CH3, -C2H5, -OCH3 or-OC2H5;;

R27', R28' and R29' independently of one another are selected from hydrogen, chloro, methyl, ethyl, methoxy or ethoxy; K1' is a group of one of formulae Kb', Kc' or Ke' to K1' defined above under K'; X' is 1,4-phenylene or a group offormula

where R40' is Cl, Br, methyl, ethyl, methoxy or ethoxy; Xa is X1, X5, X6, X7, X10, X11, X12, X16, X17, X22, X25, X26, X27, X30, X31, X49, X50, X51, X52, X53, X54, X58, X59, X62f

R41a is hydrogen, Cl, CH3 OCH3; R43a is Cl, -NHCH2CH2OH or -N(CH2CH2OH)2; Xb' is X1, X2', X2", X14', X15', X21' or X34'.

Most preferred compounds offormulal are of formula IV

where K'" is a group offormula Kb', Kd', Ke', Kf', Kg', Kh', Ki', Kk', or Ki'i or a group offormula K

where X" is 1 ,4-phenylene or a group of formula

were B40,, is Cl, methyl or methoxy; Xa" is X1,X11,X17,X27,X51,X52,X54,X64,X2',X14', X15',X19',X19",,X19'",X20',X20",X21',X32',X34',34", X34'",X34iv,X34v, X34vi.

In this specification unless indicated to the contrary any C1-6alkyl group is preferably C1-4alkyl ; any C1-4alkyl group is preferably methyl or ethyl, more preferably the former; any C1-4alkoxy group is preferably methoxy or ethoxy and any halogen is preferably chlorine or bromine, more preferably the former.

PreferablyA, when a C1-10alkylene group, is -(CH2)-a where a is an integer from 1 to 4 inclusive.

Preferably R6, when a substituted C1-6alkyl group, is C1-4alkyl monosubstituted by unsubstituted phenyl, -CONH2, CN,-COO(C1-4alkyl); more preferably

R8, when a substituted alkyl group is preferably unsubstituted benzyl.

In the above formulae: preferably p is p'; preferably R1 isR1', more preferably R1"; preferably X0 is X0', more preferably X0"; preferably R2 is R2', more preferably R2"; preferably R3 is R3, more preferably R3"; preferably R4 is R4', more preferably R4"; preferably R5 is R5, more preferably R5"; preferably R5a is R5a', more preferably R5a"; preferably B8 is Rsl, more preferably R6"; preferably R6a is R6a', more preferably R6a"; preferably R7 is R7', more preferably R7"; preferably K is K', more preferably K", most preferably K"'; preferably K1 is K1'; i most preferably K1"; preferably R13 is R13'; preferably R14 and R15 are R14' and R15'; preferably R16i is methyl; preferably R17 is R17'; preferably R18 is R18'; preferably R19 is R19'; preferably R21 is CH3; preferably R22 is R22'; preferably R23 is R23'; preferably R24 and R25 is F R24' and B25,; preferably R26 is R26'; preferably R27, R28 and R29 are R27', R28' and R29'; preferably R35 is R35'; preferably Xa is Xa'; preferably Xb is Xb' ; I more preferably a direct bond.

preferably X is X' more preferably X".

Compounds of formula I in which Kisother that K Ka, can be prepared by reacting a diazotised amine of formula V

with a coupling component H-Kwhere all the symbols are as defined above.

Coupling may be carried out by known methods.

Advantageously coupling is carrisd out in aqueous medium (in acid, neutral or alkali conditions) at temperatures from -1 0 C to room temperature, preferably in the presence of a coupling accelerator such as pyridine or urea.

Coupling components H-K(exceptwhere K is a group K)areknown ormaybe made from known compounds by known methods.

Coupling components H-Kwhere K is a group K1 can be prepared bycyclising 2 mol of a compound of formula Va NC-CHCN H-T-B0 V0 where the symbols are defined above in the presence of a substantiallywater-free organic medium (for example an alcohol) at high tempera tures in the presence of a base (for example an alcoholate). The compounds offormula Va are known or may be prepared from known compounds.

Compounds offormula I in which K is Ka may be prepared by conventional oxidative dimerisation of an amine offormula V.

Compounds offormula V can be prepared by chloromethylating dehydrothiotoluidine (or a derivativethereof) by known methods (for example as given in German Auslegeschrift 1,965,993). The chloromethylated compound is then quaternised with an R-yielding compound to give compounds offormula Vwhich are then diazotised. Chloromethylation may occur on ring B OF ring C and in practice mixtures of compounds are always obtained.

The compounds offormula I (or mixtures thereof) can be isolated from aqueous solution by known methods for example by salting out, by precipitation or concentration by evaporation.

In the compounds according to the invention the anion A0 may be exchanged for other anions, e.g.

with the aid of an ion exchanger, or by means of a reaction with salts or acids, optionally in several stages, e.g. byforming the hydroxide orthe bicarbonate, or in accordance with German Published Specification 2,001,748 or 2,001,816.

The anion A0 in non-chromophoric and may be one which is conventional in basic dyestuffchemis- try. The anion A0 is understood to include both organic and inorganic ions, e.g. halide, such as chloride or bromide, sulphate, bisulphate, methyl sulphate, aminosulphonate, perchlorate, benzenesulphonate, oxalate, maleinate, acetate, propionate, lactate, succinate, tartrate, palate, methanesulphonate or benzoate ions, or complex anions such as those of zinc chloride double salts, and furthermore the anions of the following acids: boric acid, citric acid, glycolic acid, diglycolic acid or adipic acid, or addition products of orthoboric acid with polyalcohols,e.g. cis-polyols.

The compounds according to the invention produce a pH of about7 in aqueous medium. The compounds according to the invention may be used directly as dyestuffs orthey may be used in the form of aqueous, e.g. concentrated stable solutions or as granules in quaternised form andlor in the form ofthe corresponding salts of mineral acids or organic acids, fordyeing alltypes offibre material, cellulose, cotton or leather, but especially paper or paper products and bastfibressuch as hemp,flax,sisal, jute,coirorstraw.

The dyestuffs may also be employed in the production of bulk-dyed, sized and unsized paper.

They may be similarly employedfordyeing paper by dipping. Paper, leather and cellulose can be dyed in accordance with known methods.

In paper production, the dyestuffs according to the invention and their preparations do not colour the back water at all, or only slightly which is particularly useful for purifying waste water. The dyestuffs according to the invention are highly substantive, do not give mottled dyeings when dyed on paper, and are substantially insensitive to pH. The dyeings on paper are notable for their good light fastness properties. After long-term exposure to light, the shadealterstone-in-tone. The dyed papers are wet-fast, not only to water, but also to milk, soapy water, sodium chloride solution, fruit juices, sweetened mineral water, and because oftheir good alcohol fastness, they are also resistant to alcoholic beverages; furthermore, when dyed on paper, they give a very stable shade.

The dyestuffs according to the invention may be used for dyeing, padding or printing polyacrylonitrile textiles, or polyamide or polyester textiles which are modified by anionic groups.

Inthefollowing Examples all parts and percentages are byweight and all temperatures are given in degrees Centigrade, unless indicated-to the contrary.

In the Examples where a non-integer number is given defining the number of groups present on a molecule this indicates a mixture of compounds that on average give the non-integer number given.

Example 1 249 (0.1 mol) of dehydrothiotoluidine are chlorosulphonated in known manner in chlorosulphonic acid with paraformaldehyde, the reaction conditions being selected such that the degree of chloromethylation is about 1.5. The presscake of the ch loromethylated product, which contains water, is stirred into water, and mixed with 78 g (0.45 mol) of pentamethyldiethylenetriamine. The solution is heated to 400 and stirred at this temperature for 5 hours, the pH value of the solution being kept at 10.5 to 11.0 by adding caustic soda. The suspension is rendered strongly acidic (pH 1 ) with 10 N hydrochloric acid, and then 25 ml of a 4 N sodium nitrite solution are added dropwise at 0 - 5 inca. 1 hour. The excess nitrous acid is destroyed with a little aminosulphonic acid, and any excess acid is buffered with sodium acetate. A solution of 19 g (0.05 mol) of bisacetoacetic-otoluidimide in 150 ml of dimethylformamide is added dropwise at room temperature inca. 2 hours to the diazonium salt solution thus obtained. After stirring for 6to 8 hours, hours the dyestuff is filtered off, washed with water and vacuum dried. The resulting dyestuff is a mixture of of formula 1 andla.

Due to the chosen molar ratio of chloromethyl groups to triamine being 1:3, compounds having further bridging (dimerisation) via the triamine are in practice excluded and they are of no value for dyeing, along with -SO3H and -CH20H group-containing compoundswhich are present in small quantities and are obtained upon chloromethylation or hydrolysis.

From acetic acid-containing solutions the dyestuff so obtained produces greenish-yellowdyeingon polyacryfonítríle, cotton, leather and paper. When dyeing paper,the backwater is practically colourless and the dyedpaperis notable for its excellentwet fastness.

Example 2 By a method analogeus to that of Example 1 but changing the molac ratia of chloromethyl groups two polyamine from 1:3to 1:0.3, that is 0.1 mol of chloromethylated dehy drothiotoluidine to 15 g (0.12 mol) oftetramethylpropylene diamine, and coupling with 0.1 mol of acetoaetico-aniside, a yellow dyestuff is obtained, beings mixture of compounds offormula 2 and 2a

where the bridging group Xd is

Formula 2a itself represents a mixture of compounds which vary in the number and position of the substituents and bridging groups.

The dyeings of this mixture of compounds on paper are notable again fortheir high substantivity and wet fastness.

In the following Examples the group W has the following significances:

Examples 3 to 57 Compounds of the formula

can be prepared bya method analogous to that of Examples 1 or2from appropriate starting materials, the symbols ofwhich are defined in Table 1 below; y is a number of approximately 1.5 and is bound to ring BorC.

TABLE I

Example X W , R No.

-CH3 4 do. W4 do.

S do. W5 do.

6 do. W6 do.

7 do. W7 do.

8 do. W11 do.

9 do. W12 do.

10 do. W14 do.

11 do. W1 -OCH3 12 # do. W2 do.

13 do. W3 do.

14 ! do. W8 do.

15 do. W9 do.

16 do. W10 do.

17 do. W13 do.

Table 1 continued

Example No. X W R 18 X1 W14 -OCH3 19 X1 W14 B 20 do W3 " 21 X11 W1 " 22 do W3 " 23 X5 W1 " 24 X13 W1 " 25 do W3 " 26 X70 W1 " 27 do W3 " 28 do W4 " 29 do W5 " 30 do 116 32 do W7 " 32 do W0 33 do Wg 34 do 1110 35 do W10 " 36 X71 W1 37 do W3 38 do W4 39 do 40 do W6 " 41 do W7 42 do 118 43 do W8 44 do W10 45 do W11 46 X85 W1 47 do W3 48 do W4 49 do W5 50 do 116

Example No. I X W @ R 51 X85 W7 H 52 do. W8 H 53 do. W10 H 54 do. W1 K 55 X85 W3 H 56 X82 W1 H 57 do. W3 # H Examples 58 to 78 Compounds offormula

in which R51 and Ware defined in Table 2 can be prepa by a method analogous to that of Examples 1 or 2 from approp starting materials.

Table No. 2

Examples 79 to 81 Compounds of the formula

in which the symbols are defined in Table 3 below, can be prepared from suitable starting materials by a method analogous to that of Examples 1 or2.

Example No. W 79 W1 80 W3 81 W11 Examples 82 to 83 Compounds oftheformula

in which the symbols are defined in Table 4 below, can be prepared buy a methodanalogoustothatof Examples 1 or 2 from appropriate starting materials.

Example No. R52 W K 82 CR3 W3 53S A0 t U3 U$ A3 81 CE3 W1 1i0 -CO-82-E(CHz Examples 84 to 91 Compounds of the formula

in which the symbols are defined in Table 5 below, can be prepared buy a method analogous to that of Examples 1 or2from a appropriate starting materials.

Table No. S

Example No W R53 1 R54 84 3 g3 e A0 -K 85 do -(cH2)3NCcH3)2 86 do do H 87 do do Z 5 88 do Ae -(cR3)2:(cH3)2 89 do -CN hRX 8 90 do A Ng (Cd3)2 -11 91 do t98 -H E'3 Examples 92 to 98 Compounds of the formula

in which the symbols are defined in Table 6 below, can be prepared buy a method analogous to that of Examples 1 or 2 from appropriate starting materials.

Example No. W K 92 1 ,OH 93 do N t R3 A 32 ND 94 R3 8 113 (CH2) 3U (CR3) 2 Cd2CH20H 95 W3 dCONd m (calla) 3N ( CH3) 2 C H 'e 2 5 95 113 2 4 A9 97 W1 V C2H5 \ C2Hq.

OR ,(CH2) 3N(C2H5)2 98 3 HO3 98 W3 H03::nr(CH2)3N(C25)2 NH 99 W3 (C 2)2 (CH2CH2NHoC (CH3)2N(CH2CH2NH0C 2 CH2CH2N(CH3)2 Dyeing Example A 70 Parts of chemically bleached sulphite cellulose (from pinewood) and 30 parts of chemically bleached sulphite cellulose (from birchwood) are ground in a Hollander in 2000 parts of water. 0.2 Parts of the dyestuff described in Example 1 are sprinkled into this pulp. After mixing for 20 minutes, paper is produced from this pulp. The absorbent paper obtained in this way is dyed greenish-yellow. The waste water is practically colourless.

Dyeing Example B 0.5 Parts ofthe dyestuffof Example 1 are dissolved in 100 parts of hotwater and cooled to room temperature. This solution is added to 100 parts of bchemically bleached sulphite cellulose which have been ground in a Hollanderwith 2000 parts of water.

Afterthorough mixing for 15 minutes, sizing takes place. Paper which is produced from this matter has a greenish-yellow shade of average intensity, with good wet-fastness.

Dyeing Example C An absorbent length of unsized paper is drawn through a dyestuffsolution ofthefollowing composi tion at 400 to 50 ; 0.5 parts of the dyestuff of 1; 0.5 parts of starch and 99.0 parts of water. The excess dyestuff solution is squeezed out through two rollers.

The dried length of paper is dyed greenish-yellow with good fastness.

Dyeing Example D 2 Parts ofthe dyestuff according to Example 1 are dissolved at 400 in 4000 parts of softened water. 100 parts of premoistened cotton fabric are entered into the bath, which is heatedfor30 minutes to boiling temperature. The bath is kept at boiling temperature for 1 hour,andthewaterwhich evaporates is replaced from timeto time. The dyeing is then removed from the liquor, rinsed with water and dried.

The dyestuff is absorbed practically quantitatively on thefibres; the dye bath is practically colourless. A greenish-yellow dyeing is obtained with good light fastness and good wet fastness.

In the above dyeing Examples Ato D the amount of Example 1 can be replaced by an appropriate amount of any one of the compounds of Examples 2 to 98.

Claims (9)

1. Acompound offormulal

in which R is hydrogen or unsubstituted C1 -4alkyl; K is the residue of a benzthiazolyl substituted phenyl or of a coupling component of theacetoacety- lalkylamide series, the acetoacetylarylamide series, the pyridone series, the pyridine series, the di- or tri-amino pyridine series, the pyrazolone or amino pyrazole series, the 0: or ss-naphthol series, the aminophenyl series, the indole series, the carbazole series orthe barbituric acid series; and X0 is a direct bond or non-cationic bridging group attached to K or a methylene bis-cationic bridging group attached to ring B or ring C; AO is a non-chromophoricanion; wisOto1; tisOto 1; p is 0,3 to 3, the valuesforw, t and p being average values in the case of mixtures; b is 1 or 2, provided that when b= 1, p is in the range 0.5-3 and when b=2, p is in the range 0.3 -1.5; B1 is

ris0orl; R2a is C14alkyl; R2 is a linear or branched C, 6alkyl group, unsubstituted or monosubstituted by a di(C14alkyl)amino group or by a linear or branched unsubstituted C38alkenyl group;; R3 is hydrogen, a linear or branched unsubstituted C1-6alkyl group or a linear or branched C3-6alkenyl group;

A is a direct bond or a bridging group; B5 is hydrogen, C1-6alkyl unsubstituted or monosubstituted by phenyl, -CONH2 or -COO(Cr4alkyl); C2 6alkylene monosubstituted by CN, OH or halogen; -CH2-CH#-CH2; unsubstituted cyclohexyl; or a C3 6alkenyl group unsubstituted or monosubstituted by OH or halogen.

B6 has a significance of B5 (independently of R5) of B5 and R6together with the N-atom to which they are attached form a morpholine ring unsubstituted or substituted by 1 to 3 C1-4alkyl groups, a piperazine ring unsubstituted or substituted by 1 to 3 c1-4alkyl groups, a pyrrolidine ring unsubstituted or substituted by 1 to 3 C14alkyl groups or a piperazine ring unsubstituted or substituted by 1 to 3 C14alkyl groups; R5a has a non-cyclic significance of B5 (independently of R5) except hydrogen, and R6a has a non-cyclic significance of B6 (independently of R6) except hydrogen; and R7 is a linear or branched C14alkyl, unsubstituted or mono-substituted by halogen, OH, unsubstituted phenyl or-CONH2; or R5a and R5a together with the N-atom to which they areattachedform a cyclic significance of B5 and R6; or R5a, B60 and R7 together with the N-atom to which they are attached form a pyridine group unsubstituted or substituted by 1 to3 C1-4alkyl groups; provided that when b is ,then both B5 and B6 if present are other than hydrogen.

2. Acompound offormula II

in which R' is hydrogen, methyl or ethyl,

R2a' is methyl or ethyl R2' is C1-4alkyl, unsubstituted or substituted by dimethylamino; R3' is hydrogen or unsubstituted linear or branched C1.4alkyl;

A'is a direct bond, -O-, -S-, -N- R8, -(-CH3R@)-m Y-(CH3A)-m, or a C1-12alkylene group uninterrupted or interrupted by 1 or 2 groups selected from -0-, -S-, and -N-R8 the C1-12alkylene group being unsubstituted or monosubstituted by -(CH2)rn-N(B3,)2; where mis an integerfrom Oto 6 inclusive; Y is-NH-CO-NH-, -HN-CO-(CH2)m-CONH-,

B8 is hydrogen, unsubstituted C14alkyl;; unsubstituted phenyl or unsubstituted naphthyl;

R11 is hydrogen, unsubstituted linear or branched C1-4alkyl or unsubstituted phenyl; R5' is hydrogen; CH2#-CH-CH-2-CH2-CO-CH3; linear or branched C14alkyl unsubstituted or monosubstituted by phenyl, -CON H2, -COO(C1-4alkyl); C2 4alkylene unsubstituted or monosubstituted by a group selected from Cl, Br, CN and OH; or C34alkenyl unsubstituted or monosubstituted by OH or Cl; R6' is hydrogen or linear or branched unsubstituted C1 4alkyl; or R5' and B6, together with the N-atom to which they are attached form an unsubstituted morpholine, piperidine, pyrrolidine or N-methyl piperazine group; R5a' has a non-cyclic significance of B5, except hydrogen, R6a' is unsubstituted C14alkyl and R7' is unsubstituted C14alkyl or benzyl; or R5a', R6a' and B7, together with the N-atom to which they are attached form

where z is 0,1 or 2 and R36 is methyl or ethyl;K' is Ka to K1 below

in which Ba is -N(Rra)2 or -N#(R2a)2R3a A0 Bia is hydrogen, unsubstituted phenyl, unsubstituted cyclohexyl or C1-12alkyl unsubstituted or monosubstituted by halogen, CN, OH, phenyl or-CONH2; or both R1a stogether with the N-atom to which they are attached form an unsubstituted piperidine, unsubstituted morpholine, unsubstituted piperazine, a C-unsubstituted N-(C14alkyl) piperazine or unsubstituted or unsubstituted pyrrolidine; R2a has anon-cyclic or cyclic significance of R1a except hydrogen and R3a is unsubstituted C1-6alkyl or phenyl-C1-4alkyl; or both R2a sand R3a S together with the N-atom to which they are attached form a pyridinium group, unsubstituted or substituted by 1 to 3 alkyl groups.

T is an unsubstituted C3.8alkenylene group or a linear or branched C1-12alkylene group, uniterrupted or interrupted by one -0-, -SO-or-N-R8 group; R13 is a group offormula

R14 and R15 independently of one another are unsubstituted FC1-4alkyl or unsubstituted C1-4 alkoxy; R16 is hydrogen, unsubstituted C1-4alkyl, unsubstituted benzyl or unsubstituted phenyl; R17 is hydrogen, -CN, -CONH2,

R18 is hydrogen; C1-4alkyl unsubstituted or substituted byan unsubstituted phenyl group; -(CH2)2-CN; -(CH2)2OH; -(CH2)3OCH3;

where R6a' and R7', are as defined above; B19 is hydrogen, unsubstituted C1-4alkyl, -(CH2)3OCH3, -(CH2)2OH, -(CH2)3N(CH3)2 or-( CH2)3N0(CH3)3A0; R20 is-OH or -HN2; R21 is unsubstituted C1-4alkyl or-CO-R31;

R27, R28, R29 independently of one another are selected from hydrogen, halogen, unsubstituted C14alkyl or unsubstituted C14alkoxy, -NO2 and CN; R30 is unsubstituted C14alkyl, -CON(C1-4alkyl)2 or -N(C1-4alkyl)2; nis 0,1 or 2;;

R32 and R33 independently of one anotherare selected from hydrogen, halogen, unsubstituted C1-4alkyl, unsubstituted C1-4alkoxy, -NO2 and -HN2; R34 is hydrogen or-NHCO(CH2)m-R39;

R37 and R38 independently of one another are selected from hydrogen and unsubstituted C1.4alkyl;

K1 is a group offormula Ka to Kc or Ke to Ki (as defined under K' above); Xis 1,4-phenylene, 1,5-naphthylene, 2,7-fluorene or a group offormula

where R40 is halogen, unsubstituted C1-4alkyl or unsubstituted C1-4alkoxy; Xa is any one ofX1 to X64 X1 is a direct bond, X2 is a linear or branched C14alkyl group;;

X63 -O-CH2-O-, X64 -CO-N H-R44-CO-NHwhere R41 is halogen, unsubstituted C1-4alkyl or unsubstituted C1-4alkoxy; R42 is hydrogen or unsubstituted C1-4alkyl; R43 is halogen, -NH-CH2CH2OH or N9CH2CH2OH)2; R44 is a linear or branched unsubstituted C1 4alkylene group; g is an integerfrom 1 to 4 inclusive; Xb Is X1,X2,X14,X21 or X34 defined above; Xo' is X defined above attached to K' or is Xc where Xo is a group of the formula

where R2a', A', R3' and rare as defined above, attached to ring B or ring C.

3. Acompoundofformula Ill

in which p' is 1 or 2,

R2" is -CH3, -C2H5, -(CH2)2-N(CH3)2 or -(CH2)3-N(CH3)2; R3" is hydrogen or methyl; A" is a direct bond or (CH2)a where a is an integer from 1 to4inclusive;

R5" is selected from -CH3,

R6" is selected from -CH3 or -C2H5; R5a" and R6a" have a significance of R5" and R6" respectively (independently of R5" and R6") R7" is-CH3 or C2H5; K" is a group of one of formulae Kb'to K1'

where R1a' is hydrogen or unsubstituted C1-4alkyl; R13' is

R14' and R15' independently of one another are-CH3, -C2H5, -OCH3 or-OC2H5;

R27', R28' and R29' independently of one another are selected from hydrogen, chloro, methyl, ethyl, methoxy or ethoxy;; K1' is a group of one offormulae Kb', Kc' or Kc' to K1' defined above under K'; X' is 1,4-phenylene or a group offormula

where R40' is Cl, Br, methyl, ethyl, methoxy or methoxy; Xa' is X1,X5,X6,X7,X10,X11,X12,X16,X17,X22,X25, X26,X27,X30,X31,X49,X50,X51,X52,X53,X54,X56,X59, X62,

R41a is hydrogen, Cl, CH3, OCH3; R43a is Cl, -NHCH2CH2OH or-N(CH2CH2OH)2; Xb' is X1,X2',X2",X14',X15',X21' or X34',

4. A Compound of formula IV

where K"' is a group offormula Kb', Kd', Ke', Kf', Kg', Kh',Ki', Kk' or Kl' or a group of formula Kc"

whereX" is 1,4-phenylene ora group offormula

where B40,, is Cl, methyl or methoxy;; Xa" is X1,X11,X17,X27,X51,X52,X54,X64,X2',X14', X15',X19',X19",X19'",X20',X20",X21',X32',X34',X34", X23'",X34iv,X34v,X34vi.

5. Acompound according to Claim las described in any one of the Examples.

6. A processforthe production of a compound according to Claim 1 in which K is otherthan Ka comprising the step of reacting a diazotised amine of formula V

with a coupling component H-Kwhere all the symbols are as defined in Claim 1.

7. A process for the production of a compound according to Claim 1 in which K is Ka, defined in Claim 2, comprising the step of oxidative dimerisation of an amine offormula V.

8. A substrate to which a compound of formula I defined in Claim 1 has been applied.

9. A method of dyeing a substrate comprising applying to the substrate a compound offormula I defined in Claim 1.